The capillary electrochromatographic separation performance of hydrophobic
amines and a related quaternary ammonium compound on continuous beds based
on polymers of acrylamide has been studied. The chromatographic bed is poly
merized in situ and the character of the polymers with regard to hydrophobi
city and charge has been systematically changed by regulating its content o
f isopropyl and sulfonate ligands, respectively. The best performance was o
btained for columns with a molar ratio of 1.80 for the sulfonate and isopro
pyl groups, and resulted in efficiencies up to 200 000 plates per meter. Th
e effects on retention, resolution and elution order by ionic strength, pH,
and content of acetonitrile in the mobile phase have been investigated. Th
e quaternary ammonium compound was always the least retained irrespective o
f pH. By increasing the pH, a reversal of the migration order between the t
ertiary and secondary amine was obtained. The results indicate a complex mi
gration/retention mechanism where ion-exchange, adsorption and electrophore
tic mobilities play a role. The concentration limit of detection could be l
owered from 1.3 mug/mL to 50 pg/mL by using a high content of 2-propanol (9
6%) in the sample compared to dissolving the analytes in the mobile phase.